- S Kβ x-ray fluorescence spectra of the Tl2S-Sb2S3 chalcogenide system
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The sulphur 3p valence states of Sb2S3, Tl3SbS3, TlSbS2, TlSb3S5, TlSb5S8, and Tl2S of the Tl2S-Sb2S3 system hav
- Dupont,Gheorghiu,Senemaud,Mariot,Hague,Lippens,Olivier-Fourcade,Jumas
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- ORTHO-THIOBORATES AND ORTHO-SELENOBORATES: SYNTHESIS, STRUCTURE AND PROPERTIES OF Tl3BS3 AND Tl3BSe3.
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Tl//3BS//3 and Tl//3BSe//3 were prepared as black crystalline phases by reaction of stoichiometric amounts of the elements at 800-950 degree C and subsequent annealing at 400-200 degree C. They are the first orthothio- and orthoselenoborates which have been characterized. According to single-crystal structure analyses, they contain trigonal planar BS//3**3** minus (B-S bond length 1. 83 A) and BSe//3**3** minus groups (B-Se bond length 1. 95 A). There are two structurally different thallium atoms in the structure with irregular 6 plus 1- or 6 plus 2-coordination by sulfur (selenium), the inert electron pair at Tl** plus showing strong stereochemical activity. The crystal structures of 1 and 2 are isotypic to each other but not isotypic to any other M//3AB//3 structure.
- Krebs,Hamann
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- Electronic properties of the crystalline phases of the Sb2S3-Tl2S system
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The electronic properties of the crystalline phases of the Sb2S3-Tl2S system are investigated both experi-mentally and theoretically. Experimental data obtained by x-ray photoelectron spectroscopy and 121Sb Moes
- Lippens,Olivier-Fourcade,Jumas,Gheorghiu,Dupont,Senemaud
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- INCORPORATION OF Tl IN MONOCRYSTALLINE n-PbS.
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The incorporation of Tl in monocrystalline n-PbS was studied on PbS annealed under various Tl vapor pressures and on vapor-grown PbS:Tl//2S crystals by measuring the surface concentration and in-depth distribution of thallium as well as the lattice parameter and carrier concentration. The Tl in annealed samples increases and the lattice parameter diminishes proportionally to the Tl vapor pressure. The penetration plots of Tl in PbS at 650 degree C in the concentration range up to 1 at% follow an erfc law. A model explaining the anomalous behavior of the lattice parameter and high self-compensation in PbS:Tl is proposed.
- Klimakow,Schenk,Christ
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- Thermodynamic properties and homogeneity regions of Tl6SCl 4 and Tl5Se2Cl
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In this activity system Tl-Tl2X-X (X = S, Se)are studied using emf measurements of concentration chains relative thallic electrode. The solid phase diagrams of these systems are clarified, homogeneity areas of the compounds Tl6SClsu
- Guseinov,Babanly,Sadygov,Babanly
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- Quaternary chalcogenides of the IVa metals with layered structures: Preparation and crystal structures of TlCuTIV Q3 (T = Zr, Hf; Q = S, Se) and their relation to the Re3B structure type
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The new compounds TlCuTIVQ3 (T = Zr, Hf; Q = S, Se) were prepared by reacting intimate mixtures of Tl2S or TlSe with stoichiometric amounts of the corresponding Group IV metal, Cu and the corresponding chalcogen at 870°C. The four compounds are isostructural and crystallize in Cmcm, Z = 4 with a = 3.726(4) A, b = 13.987(9) A, c = 9.783(4) A for TlCuZrS3; a = 3.847(1) A, b = 14.381(6) A, c = 10.150(1) A for TlCuZrSe3; a = 3.694(1) A, b = 14.030(3) A, c = 9.750(3) A for TlCuHfS3; and a = 3.831(1) A, b = 14.409(9) A, c = 10.124(2) A for TlCuHfSe3. Their crystal structures were determined from single crystal diffractometer data (Mo Kα radiation, ambient temperature) and refined to conventional R values of 0.016, 0.040, 0.019 and 0.031 respectively. An outstanding feature of their crystal structures is the formation of infinite anionic layers, 2∞-[CuTIVQ3]- parallel to (010), which are separated by Tl+ cations. These layers are built up by edge sharing TQ6 octahedra and distorted CuQ4 tetrahedra. Average T-Q distances are d(Zr-S) = 2.586(1) A, d(Zr-Se) = 2.707(1) A, d(Hf-S) = 2.569(2) A and d(Hf-Se) = 2.694(1) A. Cu-chalcogen distances are d(Cu-S) = 2.318(2) A and d(Cu-Se) = 2.432(3) A respectively. The thallium ions are in bicapped trigonal prismatic chalcogen coordinations. The atomic arrangement corresponds to that of KCuZrS3; based on the thallium-chalcogen partial structure it can be regarded as a filled variant of an anti-Re3B structure type.
- Klepp, Kurt O.,Gurtner, Doris
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- The effect of KI on the formation of Tl2E (E = S, Se) nanorods via solvothermal route
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Tl2E (E=S or Se) nanorods were synthesized via solvothermal route with the addition of KI. The products were characterized with X-ray powder diffraction patterns and transmission electron microscope images. Their optical properties were studied by UV-vis transmittance and photoluminescence spectrum. The band gap of direct forbidden transitions was found larger than that of bulk materials, because of the blue shift caused by nanometer-scale crystalline particles due to quantum confinement effects. A possible growth mechanism is proposed.
- Ni, Youbao,Shao, Mingwang,Wu, Zhengcui,Gao, Feng,Wei, Xianwen
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- Two new examples of very short thallium-transition metal contacts: Tl3Ag3Sb2S6 and Tl3Ag3As2S6
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Two new sulphosalts Tl3Ag3Sb2S6, (1) and Tl3Ag3As2S6, (2) were prepared in reaction of synthetic binary sulfides: argentite (Ag2S), carlinite (Tl2S) and orpiment (As2S3) or stibnite (Sb2S3), and their crystal structures have been determined using single-crystal data. The compounds are isostructural and crystallize in the space group P21/c (Z = 4), with a = 11.6854(17) ?, b = 11.8602(17) ?, c = 12.1294(18) ?, β = 123.356(2)°, V = 1404.1(4) ?3 for 1, and a = 11.4415(14) ?, b = 11.7530(15) ?, c = 11.9880(16) ?, β = 123.516(3)°, V = 1344.0(3) ?3 for 2. Refinements involving anisotropic displacement parameters for all atoms converged to the conventional R-factors: R1 = 0.0496 for 1 and R1 = 0.0372 for 2. The structures consist of two kinds of slabs alternately situated along [1 0 0] direction and sharing S atoms located between them. The first slab is built up of Tl1S8, Tl2S6, Tl3S5Ag3 coordination polyhedra and Ag3S3Tl3 distorted trigonal pyramid (the average 〈Ag3-S〉 distance is 2.542 for 1 and 2.539 ? for 2) combined with trigonal Sb1S3 or As1S3 coordination pyramids (〈Sb1-S〉 and 〈As1-S〉 are 2.438 and 2.259 ?, respectively). The thallium atom Tl1 is surrounded by eight S atoms forming a square anti-prism (〈Tl1-S〉: 3.393 for 1 and 3.356 ? for 2), while the coordination polyhedron of Tl2 can be described as a significantly distorted trigonal prism or as an extremely distorted octahedron (〈Tl2-S〉: 3.236 ? for 1 and 3.238 ? for 2). Thallium Tl3 is surrounded by six atoms (one Ag, four S at shorter and one S at longer distance), which form a distorted trigonal prism (〈Tl3-S〉: 3.165 ? in 1 and 3.155 ? in 2). The second slab consists of trigonal Sb2S3 or As2S3 coordination pyramids combined with Ag1S4 and Ag2S4 coordination tetrahedra (〈Sb2-S〉 and 〈As2-S〉 are 2.433 and 2.251 ?, respectively; 〈Ag1-S〉: 2.623 ? for 1 and 2.612 ? for 2; 〈Ag2-S〉: 2.623 ? for 1 and 2.630 ? for 2). The most interesting feature of both structures is the existence of short Tl3-Ag3 contacts of 2.959(2) ? in 1 and 2.922(1) ? in 2. These contacts are the shortest found so far and indicate very strong Tl-Ag interactions. They are discussed in terms of metallophilicity principle and relativistic effects. It is also pointed out that if only valence shell electrons are considered (Tl-Ag)2+ group is isoelectronic with the (Hg-Hg)2+ ion, therefore new examples of short Tl-Ag contacts could be expected.
- Karanovi?, Ljiljana,Poleti, Dejan,Bali?-?uni?, Ton?i,Makovicky, Emil,Gr?eti?, Ivan
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- Raman spectroscopic study of the ternary system Sb2S3-As2S3-Tl2S
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Raman spectroscopy has been used to study the local structure in glassy compositions of the ternary system As2S3-Sb2S3-Tl2S. The evolution of the positions and shapes of the bands observed is attribut
- El Idrissi Raghni,Bonnet,Hafid,Olivier-Fourcade,Jumas
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- Tl2S-Sb2S3-Bi2S3 quasi-ternary system
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The Tl2S-Sb2S3-Bi2S3 quasi-ternary system (system A) was studied using DTA, X- ray powder diffraction, microstructure examination, and microhardness measurements. TlSbS2-Tl4Bisu
- Dzhafarov, Ya. I.,Babanly
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- Synthesis and crystal structure of Cu4TiS4: A novel chalcogenide with tetrahedrally coordinated titanium
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Dark red single crystals of Cu4TiS4 were prepared by reacting an intimate mixture of Cu2S, Ti and S at 500°C. Cu4TiS4 is tetragonal, space group I42m with a = 5.448(1) A, c = 10.565(2) A, Z = 2. The crystal structure is of a new type. It was determined from diffractometer data and refined to a conventional R of 0.024 for 132 Fos and 17 variables. The crystal structure is based on a cubic close packing of chalcogen with Cu and Ti in tetrahedral interstices. This results in a three-dimensional framework of vertex sharing CuS4 tetrahedra which are connected with the almost regular TiS4 tetrahedra through common edges. The bond lengths are d(Ti-S) = 2.278 A and d(Cu-S) = 2.333 to 2.351 A.
- Klepp, Kurt O.,Gurtner, Doris
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- Far infrared transmission study of the ternary system Sb2S3-As2S3-Tl2S
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The local environment of metal (arsenic and antimony) atoms in amorphous samples of the ternary system As2S3-Sb2S3-Tl2S has been studied by far infrared transmission spectroscopy. Variations in shape
- El Idrissi-Raghni,Durand,Bonnet,Hafid,Olivier-Fourcade,Jumas
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- Anagostic, mono- and hexahapta interactions in Tl(I) dithiocarbamates: A new precursor for the preparation of Tl2S nanoparticles
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Two new homoleptic complexes, [Tl(bzfdtc)]2 (1) and [Tl(bu2-OHbzdtc)]2 (2) (where bzfdtc = N-benzyl-N-furfuryldithiocarbamate and bu2-OHbzdtc = (N-butyl-N-(2-hydroxybenzyl)dithiocarbamate), have been prepared an
- Gomathi, Govindaraju,Thirumaran, Subbiah,Ciattini, Samuele
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- Tl2S: Re-determination of crystal structure and stereochemical discussion
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The crystal structure of synthetic carlinite, Tl2S, was redetermined by single crystal and powder X-ray diffraction methods. The cell parameters obtained from Rietveld refinement are a = 12.150(2) A, c = 18.190(4) A, V= 2325.5(7) A3. A single crystal data refinement proved Tl2S crystallizing in the trigonal space group R3 with M = 440.8gmol-1, Z = 27, R = 0.076, and wR = 0.145. The atomic arrangement found is that of a strongly deformed anti-CdI2 type, but the deformation is clearly different from that given by previous workers. In the five crystallographically different STl6 octahedra the S-Tl distances vary between 2.82 and 3.09 A, the Tl-Tl edges between 3.52 and 4.58 A. The common features of these octahedra are (i) each one with a definitely smaller vs larger Tl3 face in transposition, both faces parallel or sub-parallel (00.1), and (ii) each three shorter and longer S-Tl distances to the atoms of the larger and smaller Tl3 faces, respectively. The Tl-Tl contacts between different Tl2S sheets are on the average definitely shorter than the ones within the sheet and they can be smaller than the Tl-Tl contacts in the small Tl3 faces of the STl6 octahedra. The atomic arrangement indicates that the single electron pairs of the monovalent Tl atoms are not arranged all parallel to the z-axis, as one would expect for Tl2S with an ideal anti-CdI2 structure. The surrounding of the S atoms resembles that of one-third of the Cl atoms in yellow InCl. The absorbance of Tl2S is very low at wave numbers approximately -1.
- Giester,Lengauer, Christian L.,Tillmanns,Zemann
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- The phase equilibria in the Tl-S-I system and electrical properties of the Tl6SI4 and TlS compounds
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The phase equilibria in the ternary Tl-S-I system were investigated experimentally by means of powder X-ray diffraction (PXRD) and differential thermal analysis (DTA). Five isopleth sections, liquidus surface projection and room temperature isothermal sec
- Babanly, Dunya M.,Aliev, Ziya S.,Huseynov, Qorkhmaz M.,Asadov, Salim M.,Mustafaeva, Solmaz N.,Tagiyev, Dilgam B.
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p. 495 - 503
(2018/11/06)
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- The first scorpionate ligand based on diazaphosphole
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The reaction of PhBCl2 with 1H-1,2,4-λ3-diazaphosphole in the presence of NEt3 gives a new scorpionate ligand, phenyl-tris(1,2,4-diazaphospholyl)borate (PhTdap). The coordination behaviour of this ligand toward transition and non-transition metals has been comprehensively studied. In the thallium(i) complex, Tl(PhTdap), κ2-N,N bonding supported with intramolecular η3-phenyl coordination has been observed in the solid state. Tl(PhTdap) also shows unusual intermolecular π-interactions between five-membered diazaphosphole rings and the thallium atom giving infinite molecular chains in the crystal. In the square planar complex [Pd(C,N-C6H4CH2NMe2)(PhTdap)], κ2-bonded scorpionate has been detected in both solution and in the solid state. For other studied compounds with the central metal ion Ti(iv), Mo(ii), Mn(i), Fe(ii), Ru(ii), Co(ii), Co(iii), Ni(ii) and Cd(ii), the κ3-N,N,N coordination pattern was observed. Electronic properties of PhTdap and its ligand-field strength were elucidated from UV-Vis spectra of transition-metal species. The CH/P replacement on going from tris(pyrazolyl)borate to the ligand PhTdap causes a slight increase in electronic density rendered to the central metal atom. The following order of ligand-field strength has been established: HB(3,5-Me2pz)3 3 3 PhB(1,2,4-triazolyl) PhTdap. The crystal structures of ten metal complexes bearing the new ligand are reported. The possibility of PhTdap coordination through the phosphorus atom is also briefly discussed.
- Mlate?ek, Martin,Dostál, Libor,R??i?ková, Zdeňka,Honzí?ek, Jan,Holubová, Jana,Erben, Milan
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p. 20242 - 20253
(2015/12/01)
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- Phase diagram of the Tl-TlI-S system and thermodynamic properties of the compound Tl6SI4
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Phase equilibria in the Tl-TlI-S composition region of the Tl-S-I system were studied by dif- ferential thermal analysis, x-ray powder diffraction, and measurements of the microhardness and the emf of concentration circuits relative to a thallium electrode. A series of polythermal sections, an isothermal section at 300 K, and a projection of the liquidus surface were constructed. Primary crystallization regions of six phases, including the ternary compounds Tl6SI4 and Tl3SI, were outlined, and the types and coordinates of non- and monovariant equilibria were determined. It was shown that the ternary compound Tl6SI4 forms tie lines with Tl, TlI, Tl2S, Tl4S3, and TlS in the subsolidus region and that the homogeneity region of Tl6SI4 below 400 K does not exceed 1 mol %. From the emf measurement data, the standard thermodynamic functions of formation and standard entropy of the compound Tl6SI4 were calculated: ΔG0 f,298;= -601.7 ± 2.5 kJ/mol, ΔH0 f,298;= -595.1 ± 4.0 kJ/mol, and S0298 = 672 ± 10 J/(mol K). Pleiades Publishing, Ltd., 2012.
- Babanly,Guseinov,Babanly,Sadygov
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- Preparation, crystal structure, physical properties and electronic band structure of TlScQ2 (Q = S, Se and Te)
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The title compounds were prepared by reaction of Tl2Q (Q = S, Se and Te) Sc and Q in the temperature range of 200 to 500 °C. The structures of the selenide and the telluride adopt the α-NaFeO2 type, while TlScS2 crystallizes in the β-RbScO2 type structure. The space group is R3m for TlScSe2 and TlScTe 2 with a = 3.9370(4) A, c = 23.194(5) A, and a = 4.2129(4) A, c = 24.099(3) A, respectively. The sulphide crystallizes in P63/mmc with a = 3.761(3) A and c = 14.942(4) A. The crystal chemical relations between the three chalcogenides are discussed. According to the electrical measurements and the band structure calculations, the compounds are semiconductors or poor metals.
- Teske, Christoph L.,Bensch, Wolfgang,Mankovsky, Sergey,Ebert, Hubert
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p. 445 - 451
(2009/03/12)
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- Phase Equilibria in the Tl2S-Tl2Te-Tl 9BiTe6-TlBiS2 system
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The phase equilibria in the Tl2S-Tl2Te-Tl 9BiTe6-TlBiS2 system have been studied by differential thermal analysis and x-ray diffraction. The results have been used to construct the T-x phase diagram a
- Jafarov,Rzaeva,Babanly
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p. 1183 - 1186
(2009/05/30)
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- Phase equilibria of the Tl2S-Tl2Se-TlI system
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Phase equilibria of the Tl2S-Tl2Se-TlI ternary system are investigated by DTA and X-ray powder diffraction techniques using mathematical modeling. Phase diagrams for the Tl2S-Tl2Se, Tl2S-Tl5Se2I, and Tl6SI4-Tl 6SeI4 quasi-binary joins as well as the Tl 3SI-Tl5Se2I polythermal section are constructed. The character of physicochemical processes at invariant points is described.
- Barchii,Peresh,Sabov,Gaborets,Kun
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p. 1568 - 1571
(2008/10/08)
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- Tl4Re6X12 (X = S, Se): Crystal growth, structure, and properties
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Single crystals of two new phases Tl4Re6S12 and Tl4Re6Se12 isostructural with (Rb,K)4Re6Se12 were synthesized by high-temperature reaction of TlX, Re, and X (X = S, Se). The structure of the selenide was solved by single-crystal X-ray investigation (space group C2/c, R = 0.08). The structure consists of Re6Se8 cluster units interconnected three-dimensionally by four Se and two Se2 bridges. Tl4Re6S12 is isostructural with Tl4Re6Se12. The cell parameters of Tl4Re6S12 and Tl4Re6Se12 are a = 16.653 (2) ?, b = 9.574 (3) ?, c = 11.816 (8) ?, β = 90.62 (2)° and a = 17.177 (3) ?, b = 9.846 (2) ?, c = 12.195 (2) ?, β = 90.71 (2)°, respectively. Z = 4 for both compounds. Physical measurements show that these compounds are semiconducting and diamagnetic, which is consistent with 24 electrons per cluster unit filling the valence band. Bond-order calculations of Tl4Re6Se12 and other related compounds indicate a Re-Re bond order of 1 in all of the known Re6X8 cluster compounds.
- Huan,Greaney,Tsai,Greenblatt
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p. 2448 - 2451
(2008/10/08)
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- LOW-TEMPERATURE RHOMBIC MODIFICATION OF THALLIUM (I) SULFIDE.
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Tl//2S monocrystals of the rhombic modification were obtained by recrystallization of the powdery thallium sulfide, precipitated from solution with hydrogen sulfide, under an ammonium sulfide solution in a closed ampoule for several months at room temperature. X-ray investigations of the obtained crystals in a KFOR camera confirmed the monocrystalline nature and made it possible to determine the parameters of the rhombic elementary cell.
- Chaus,Krasan,Kompanichenko,Andreichenko
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p. 109 - 110
(2008/10/08)
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